CHAPTER 2: PARTICLE IN A CENTRAL POTENTIAL.

THE HYDROGEN ATOM

(From Cohen-Tannoudji, Chapter VII)
A. STATIONARY STATES OF A PARTICLE IN A CENTRAL POTENTIAL
We will be dealing with the following three topics:
A) Stationary states of a particle in a central potential
V(r) is invariant under any rotation about the origin, that is

H, L
k

= 0, and thus
the eigenfunctions of

L
2
and

L
z
are also eigenfunctions of H.
B) Motion of the center of mass and relative motion for a system of two inter-
acting particles
(i) a two particle system in which interaction energy depends only on the particles
relative position can be replaced by a simpler problem of one ctitious particle;
(ii) in addition, when the interaction depends only on the distance between parti-
cles, then the ctitious particles motion is governed by a central potential.
C) Exactly solvable problems
(i) V(r) is a Coulomb potential: hydrogen, deuterium, tritium, He
+
,Li
+
;
(ii) V(r) is a quadratic potential: isotropic three-dimensional harmonic oscillator.
1. Outline of the problem
a. REVIEW OF SOME CLASSICAL RESULTS
Force on the particle located at the point M

F =

V(r) =
dV
dr
r
r
(2.1)
is always directed to the origin O. In this case the angular momentum theorem
implies that the angular momentum

L = r p is a constant of motion:
d

L
dt
=

0 (2.2)
and the particle trajectory is on the plane through the origin and perpendicular to

L.
Let us consider now the position and velocity of the particle at time t. The velocity
can be decomposed into the radial v
r
and tangential velocity v

dened through the

relations
v
r
=
dr
dt
(2.3)

r v

= r

(2.4)
so that the modulus of the angular momentum is given as

r v

= r

(2.5)
The total energy of the particle
E =
1
2
v
2
+ V(r) =
1
2
v
2
r
+
1
2
v
2

+ V(r) (2.6)
can be rewritten as
E =
1
2
v
2
r
+

L
2
2r
2
+ V(r) (2.7)
which follows from

L
2
=

L
2

=
2
r
2

2
= r
2
p
2
(2.8)
The classical Hamiltonian of the system is then
H =
p
2
r
2
+

L
2
2r
2
+ V(r) (2.9)
where the momentum
p
r
=
dr
dt
(2.10)
is conjugate to the radial coordinate r, and

L
2
can be expressed using the spherical
coordinates r, and as

L
2
= p
2

+
1
sin
2

p
2

(2.11)

L
2
is a constant of motion as V(r) depends only on r and not on and that is
the kinetic energy associated with tangential motion T

=
1
2
v
2

is a constant in the
Hamiltonian. That is

L
2
plays the role of a parameter
dp
r
dt
=
d
2
r
dt
2
=
H
r
=

L
2
r
3

dV
dr
(2.12)
and this allows us to regard this problem as equivalent to a one-dimensional problem
(with 0 r < ) with a particle of mass in the effective potential
V
e
(r) = V(r) +

L
2
2r
2
(2.13)
b. THE QUANTUM MECHANICAL HAMILTONIAN
The eigenvalue problem in the coordinate representation is given as
_

2
2
+ V(r)
_

= E

(2.14)
where the Laplacian in spherical coordinates is
=
1
r

2
r
2
r +
1
r
2
_

2
+
1
tan

+
1
sin
2

2
_

_
(2.15)
Recall that

L
2
=
2
_

2
+
1
tan

+
1
sin
2

2
_

_
(2.16)
and you can write down the quantum mechanical Hamiltonian in the form analogous
to the one we found in the classical case

H =

2
2
1
r

2
r
2
r +
1
2r
2

L
2
+ V(r)
The eigenvalue equation then becomes
_

2
2
1
r

2
r
2
r +
1
2r
2

L
2
+ V(r)
_

_
(r, , ) = E(r, , ) (2.17)
2. Separation of Variables
a. ANGULAR DEPENDENCE OF THE EIGENFUNCTIONS
The three components of the angular momentum operator

L act only on the angular

variables and and thus they commute with all operators that depend on r only. In
addition they commute with

L
2
, so the three components of the angular momentum
are constants of motion:

H,

= 0 (2.18)
Obviously also

H,

L
2

= 0, so we can choose the complete set of commuting ob-

servables to be represented by the operators

H,

L
2
, and

L
z
We therefore require the eigenfunctions (r, , ) to be simultaneous eigenfunctions
of this C.S.C.O. Their eigenvalue equations

= E

(2.19)

L
2

= l(l + 1)
2

(2.20)

L
z

= m

(2.21)
now constitute a system of differential equations that must be solved simultaneously.
We know the general form of the eigenfunctions of

L
2
and

L
z
for a xed value of the
quantum numbers l and m which is given by the spherical harmonics Y
m
l
(, ). Thus
the general solution will be of the following form

= R(r)Y
m
l
(, ) (2.22)
and the remaining problem is to determine the radial function R(r) such that

is
an eigenfunction of

H.
b. THE RADIAL EQUATION
Inserting

= R(r)Y
m
l
(, ) into the eigenvalue equation
_

2
2
1
r

2
r
2
r +
1
2r
2

L
2
+ V(r)
_

_
(r, , ) = E(r, , ) (2.23)
we can formulate the eigenvalue equation for the function of the radial coordinate
R(r) only
_

2
2
1
r
d
2
dr
2
r +
l(l + 1)
2
2r
2
+ V(r)
_

_
R(r) = ER(r) (2.24)
We note at this point that the Laplacian is not necessarily dened at r = 0. In order
for

= R(r)Y
m
l
(, ) to be the solution of the eigenvalue problem, we need to
make sure that the behavior of the solutions R(r) at r = 0 is sufciently regular.
Now we face the eigenvalue problem, i.e. represented by a differential equation,
which depends only on r and l as parameters, i.e. we are looking for eigenvalues
and eigenvectors of

H
l
which is different for different values of l.
In the state space E
r
, we consider subspaces E(l, m) for xed values of l and m, and
study the eigenvalue equation of

H in each of these subspaces:
- the equation is the same in the (2l + 1) subspaces E(l, m) associated with l;
- E
k,l
are eigenvalues of

H
l
in a given E(l, m), and they can be discrete or continuous
depending on k which represents various eigenvalues with the same value of l;
- R
k,l
(r) are eigenfunctions of

H
l
in E(l, m).
The eigenvalue equation (i.e. the differential equation)
_

2
2
1
r
d
2
dr
2
r +
l(l + 1)
2
2r
2
+ V(r)
_

_
R
k,l
(r) = E
k,l
R
k,l
(r) (2.25)
can be satised by taking
R
k,l
(r) =
1
r
u
k,l
(r) (2.26)
and by multiplying both sides of the equation by r

2
2
d
2
dr
2
+
l(l+1)
2
2r
2
+ V(r)

u
k,l
(r) = E
k,l
u
k,l
(r)
Note that the last two terms in the square bracket constitute the effective potential
V
e
(r) = V(r) +
l(l + 1)
2
2r
2
(2.27)
As r 0 then l(l + 1)
2
/2r
2
0 and thus the term l(l + 1)
2
/2r
2
always repels the
particle from the origin. We call this term centrifugal potential.
Examples of V
e
for l = 0, 1, 2:
c. BEHAVIOR OF THE SOLUTIONS OF THE RADIAL EQUATION AT THE ORIGIN
We have to examine the behavior of R(r) at r = 0 to know whether they really are
solutions of the eigenvalue problem. We assume
V(r) is for r 0 either nite or approaches innity less rapidly than
1
r
;
for r 0 the radial function R
k,l
(r) Cr
s
Substituting R
k,l
(r) into the eigenvalue equation
_

2
2
1
r
d
2
dr
2
r +
l(l + 1)
2
2r
2
+ V(r)
_

_
R
k,l
(r) = E
k,l
R
k,l
(r) (2.28)
we get

2
2
1
r
d
2
dr
2
r(Cr
s
) +
l(l + 1)
2
2r
2
(Cr
s
) + V(r)(Cr
s
) = E
k,l
(Cr
s
) (2.29)

2
2
(s + 1) s r
s2
+
l(l + 1)
2
2
r
s2
+ V(r)r
s
= E
k,l
r
s
(2.30)
and setting the coefcients of the dominant term to zero we get
s(s + 1) + l(l + 1) = 0 (2.31)
The equation s(s + 1) + l(l + 1) = 0 has two solutions

either s = l
or s = (l + 1)
(2.32)
that is, for a given E
k,l
, there are therefore two linearly independent solutions of the
eigenvalue equation above behaving at r 0 like
1. r
l
, or
2.
1
r
l+1
.
However we have to reject the solution
1
r
l+1
as this diverges for r = 0 and is thus
physically unacceptable.
The acceptable solution of the eigenvalue problem converges to zero at r = 0 for all
values of l (recall that R
k,l
(r) =
1
r
u
k,l
(r)):
u
k,l
(r)

r0 Cr
l+1
(2.33)
Consequently, to the eigenvalue equation we have to add a condition
u
k,l
(0) = 0.
3. Stationary states of a particle in a central potential
a. QUANTUM NUMBERS
Summary:
The eigenfunctions of

H are required to be the simultaneous eigenfunctions of

L
2
and

L
z
which determines their angular dependence

k,l,m

= R
k,l
(r)Y
m
l
(, ) =
1
r
u
k,l
(r)Y
m
l
(, ).
The eigenvalue equation of

H is replaced by a differential equation involving only
the radial coordinate r and depending on a parameter l.
In addition:
In principle the functions (r, , ) must be square integrable

k,l,m
(r, , )

2
r
2
dr d = 1 (2.34)
and we can separately integrate their radial and angular component

k,l,m
(r, , )

2
r
2
dr d =

0
r
2
dr

R
k,l
(r)

Y
m
l
(, )

2
(2.35)
The spherical harmonics Y
m
l
(, ) are already normalized, so the normalization con-
dition reduces to

0
r
2
dr

R
k,l
(r)

2
=

0
dr

u
k,l
(r)

2
= 1 (2.36)
We note that if the spectrum has a continuous part, i.e. k is a continuous index, then

0
r
2
dr R

,l
(r)R
k,l
(r) =

0
dr u

,l
(r)u
k,l
(r) =

(2.37)
where

is -function. Since this is not a square integrable function, the nor-

malization integral diverges for k = k

.
An eigenfunction

k,l,m

= R
k,l
(r)Y
m
l
(, )
depends on three parameters as it is a simultaneous eigenfunction of

H,

L
2
and

L
z
with eigenvalues E
k
, l(l + 1)
2
, and m.
We call these parameters - k, l and m - quantum numbers:
k - a radial quantum number,
l - an azimuthal quantum number,
m - a magnetic quantum number.
The radial part R
k,l
(r) =
1
r
u
k,l
(r) of
k,l,m

are independent of m and are given by

the eigenvalue equation

2
2
d
2
dr
2
+
l(l+1)
2
2r
2
+ V(r)

u
k,l
(r) = E
k,l
u
k,l
(r)
The angular part depends only on l and m, and it does NOT depend on the form of
the potential V(r).
b. DEGENERACY OF THE ENERGY LEVELS
(2l + 1) orthogonal functions
k,l,m

with k and l xed and m varying from l to +l

are eigenfunctions of

H with the same eigenvalue E
k,l
.
That is E
k,l
is at least (2l + 1)-fold degenerate. This is called essential degeneracy
as it exists for all V(r) and is due to the fact that

H depends on

L
2
but not on

L
z
.
It is also possible that E
k,l
= E
k

,l
for l l

. This occurs for certain potentials and it

is called accidental degeneracy.
Remarks:
For a xed l, the radial equation has at most one solution which is physically accept-
able. This is ensured by the condition u
k,l
(0) = 0.
The behavior of the solutions as r follows from the behavior of the potential
V(r ) 0. The negative values of E
k,l
form a discrete set.
B. MOTION OF THE CENTER OF MASS AND RELATIVE MOTION FOR A SYS-
TEM OF TWO INTERACTING PARTICLES
1. Motion of the center of mass and relative motion in classical mechanics
Let us consider two spinless particles with masses m
1
and m
2
and positions r
1
and
r
2
respectively, and assume that the force between the particles is derived from the
potential V(r) = V(r
1
r
2
).
in classical mechanics the system is described by the Lagrangian

r
1
,

r
1
; r
2
,

r
2

= T V =
1
2
m
1

r
2
1
+
1
2
m
2

r
2
2
V

r
1
r
2

. (2.38)
The momental of the particles are
p
1
= m
1

r
1
(2.39)
p
2
= m
2

r
2
(2.40)
The study of the motion of the two particles is simplied by introducing
(i) center of mass coordinates
r
G
=
m
1
r
1
+ m
2
r
2
m
1
+ m
2
(2.41)
(ii) relative coordinates
r = r
1
r
2
(2.42)
where
r
1
= r
G
+
m
2
m
1
+ m
2
r (2.43)
r
2
= r
G

m
1
m
1
+ m
2
r (2.44)
The Lagrangian can now be rewritten as follows

r
G
,

r
G
; r,

r

=
1
2
m
1

r
G
+
m
2
m
1
+ m
2

2
+
1
2
m
2

r
G

m
1
m
1
+ m
2

2
V

r

=
1
2
M

r
2
G
+
1
2

r
2
V

r

(2.45)
where M is the total mass of the systemand is the reduced mass (i.e. the geometric
mean of m
1
and m
2
):
M = m
1
+ m
2
(2.46)
=
m
1
m
2
m
1
+ m
2
(2.47)
1

=
1
m
1
+
1
m
2
(2.48)
Conjugate momenta are the total momentum and the relative momentum dened as
p
G
= M

r
G
= m
1

r
1
+ m
2

r
2
= p
1
+ p
2
(2.49)
p =

r =
m
2
p
1
m
1
p
2
m
1
+ m
2
(2.50)
p

=
p
1
m
1

p
2
m
2
(2.51)
The classical Hamiltonian and the equations of motion are
H

r
G
, p
G
; r, p

=
p
2
G
2M
+
p
2
2
+ V

r

(2.52)

p
G
=

0 (2.53)

p =

V

r

(2.54)
where
p
2
G
2M
is the kinetic energy of a ctitious particle with mass M and position in the
center of mass which is, as indicated by

p
G
=

0, in uniform rectilinear motion.

In the center of mass frame (which is in uniform rectilinear motion

p
G
=

0) the total
momentum p
G
= 0 so the Hamiltonian reduces to
H
r
=
p
2
2
+ V

r

(2.55)
which characterizes the energy associated with the relative motion of the two parti-
cles.
Here a new ctitious particle, relative particle, is introduced with the mass (the
reduced mass of the original particles) and the relative coordinate r and momentum
p. This relative particle behaves as being a subject of a potential V(r) equal to the
potential energy of interaction between two real particles.
The study of the relative motion of two interacting particles reduces to study
of a motion of a single ctitious particle characterized by , r and p.
2. Separation of variables in quantum mechanics
a. OBSERVABLES ASSOCIATED WITH THE CENTER OF MASS AND THE REL-
ATIVE PARTICLE
The observables

R
1
,

R
2
,

P
1
, and

P
2
satisfy the canonical commutation relations, e.g.
the x components (similarly relations hold for the other components)

X
1
,

P
1x

= i (2.56)

X
2
,

P
2x

= i (2.57)
We can dene new coordinates and momenta

R
G
=
m
1

R
1
+ m
2

R
2
m
1
+ m
2
(2.58)

R =

R
1

R
2
(2.59)

P
G
=

P
1
+

P
2
(2.60)

P =
m
2

P
1
m
1

P
2
m
1
+ m
2
(2.61)
which satisfy the following commutation relations, e.g. the x components (and simi-
larly for the other components)

X
G
,

P
Gx

= i (2.62)

X,

P
x

= i (2.63)
b. EIGENVALUES AND EIGENFUNCTIONS OF THE HAMILTONIAN
The Hamiltonian

H =

P
2
1
2m
1
+

P
2
2
2m
2
+ V

R
1

R
2

(2.64)
can be rewritten in terms of the new coordinates as

H =

P
2
G
2M
+

P
2
2
+ V

(2.65)
This can be expressed as the sum

H =

H
G
+

H
r
(2.66)
where

H
G
=

P
2
G
2M
(2.67)

H
r
=

P
2
2
+ V

(2.68)

H
G
and

H
r
commute

H
G
,

H
r

= 0 (2.69)
and thus satisfy the eigenvalue equations with the common eigenvector

H
G
| = E
G
| (2.70)

H
r
| = E
r
| (2.71)
which imply that

H| = E| (2.72)
where
E = E
G
+ E
r
(2.73)
Consider {|r
G
, r} representation with the basis vectors common to the observables

R
G
and

R, (r
G
, r):

R
G
(r
G
, r) = r
G
(r
G
, r) (2.74)

R(r
G
, r) = r(r
G
, r) (2.75)
The conjugate momenta are

P
G
=

G
(2.76)

P =

(2.77)
The state space factorizes into the tensor product E = E
r
G
E
r
and the Hamiltonians

H
G
and

H
r
appear as extensions to E acting on E
r
G
and E
r
respectively.
This implies
| = |
G
|
r
(2.78)
where

H
G
|
G
= E
G
|
G

|
G
E
r
G
(2.79)
and

H
r
|
r
= E
r
|
r

|
r
E
r
(2.80)
(i) The eigenvalue equation

2
2M

G

G

r
G

= E
G

G

r
G

(2.81)
describes the motion of a free ctitious particle and has the solution

r
G

=
1
(2)
3/2
e
i

p
G
r
G
(2.82)
whose energy is
E
G
=
p
2
G
2M
0 (2.83)
(ii) The eigenvalue equation
_

2
2
+ V

r

= E
r

(2.84)
describes the behavior of the two interacting particles in the center of mass frame
(which is equivalent to a single ctitious relative particle in central potential).
The interaction depends only on the distance between the particles

r
1
r
2

and not
on the direction of r
1
r
2
.
The relative particle is subject to a central potential V(r).
The total angular momentum of the system of two real particles is given as

J =

L
1
+

L
2
(2.85)

L
1
=

R
1

P
1
(2.86)

L
2
=

R
2

P
2
(2.87)
and it can be written as

J =

L
G
+

L (2.88)
where

L
G
=

R
G

P
G
(2.89)

L =

P (2.90)
such that

L
G
,

= 0 and their components satisfy the standard angular momentum

commutation relations.
C. THE HYDROGEN ATOM
1. Introduction
The hydrogen atom is the system of two particles: proton, with mass m
p
and charge
q, and electron, with mass m
e
and charge q
m
p
= 1.7 10
27
kg (2.91)
m
e
= 0.9 10
30
kg (2.92)
q = 1.6 10
19
Coulomb (2.93)
interacting via the Coulomb potential
V(r) =
q
2
4
0
1
r
=
e
2
r
(2.94)
which depends on the distance r between proton and electron
The Hydrogen atom in the center of mass coordinate system:
Classically the Hamiltonian for the relative motion of the particles is
H

r, p

=
p
2
2

e
2
r
(2.95)
with the reduced mass
=
m
e
m
p
m
e
+ m
p
m
e

1
m
e
m
p

(2.96)
where m
e
/m
p
1/1800, so the center of mass is in almost in the same place as the
proton and thus the relative particle can be identied with the electron.
2. The Bohr model
Niels Bohr postulated xed classical orbits for motion of electron around proton
E =
1
2
v
2

e
2
r
(2.97)
The force, given as acceleration of circular motion, equals to the Coulomb force
v
2
r
=
e
2
r
2
(2.98)
The quantization condition introduced empirically by Bohr is
vr = n; where n is a positive integer (2.99)
implies (homework: derive these relations)
E
n
=
1
n
2
E
I
(2.100)
(2.101)
r
n
= n
2
a
0
(2.102)
(2.103)
v
n
=
1
n
v
0
(2.104)
The values of the introduced constants are
E
I
=
e
4
2
2
(2.105)
a
0
=

2
e
2
(2.106)
v
0
=
e
2

(2.107)
E
I
13.6 eV (2.108)
a
0
0.52 (2.109)
The Bohr model yielded the correct values for the energy levels of the hydrogen
atom. Moreover, it provides correct value of the ionization energy E
I
and the Bohr
radium a
0
and thus correctly characterizes atomic dimensions.
However, its classical character prevents it to be the ultimate theory of the hydrogen
atom which would be free of internal inconsistencies.
Quantum theory of the hydrogen atom is free of these inconsistencies.
3. Quantum mechanical theory of the hydrogen atom
Relative motion of the proton and electron is studied in the center of mass in which
the eigenvalue equation has the following form
_

2
2

e
2
r
_

= E

(2.110)
The eigenfunctions

k,l,m

=
1
r
u
k,l
(r)Y
m
l
(, ) (2.111)
where u
k,l
(r) satises
_

2
2
d
2
dr
2
+
l(l + 1)
2
2r
2

e
2
r
_

_
u
k,l
(r) = Eu
k,l
(r) (2.112)
and the condition
u
k,l
(0) = 0 (2.113)
The spectrum include dicrete and continuous parts, for example:
a. CHANGE OF VARIABLES
It is convenient to work with dimensionless quantities which we dene as
= r/a
0
(2.114)

k,l
=

E
k,l
/E
I
(2.115)
The radial eigenvalue equation becomes
_

_
d
2
d
2

l(l + 1)

2
+
2

2
k,l
_

_
u
k,l
() = 0 (2.116)
b. SOLVING THE RADIAL EQUATION
We will seek the solution by expanding u
k,l
() in power series but rst we will have a
look at its asymptotic behavior.
. Asymptotic behavior
For the terms in the eigenvalue equation above proportional to 1/ and 1/
2
are much smaller than
2
k,l
, so we can neglect them obtaining
_

_
d
2
d
2

2
k,l
_

_
u
k,l
() = 0 (2.117)
At this limit the solution therefore is e

k,l
.
If we consider the full eigenvalue equation, including the terms proportional to 1/
and 1/
2
, we expect the solution to be given by e

k,l
multiplied by a power of .
We note the solution e
+
k,l
must be rejected as it is not bounded at , and we
are left with e

k,l
as the only physically acceptable asymptotic solution.
The solution we are looking for is thus given as
u
k,l
() = e

k,l
y
k,l
() (2.118)
where y
k,l
() must satisfy the equation
_

_
d
2
d
2
2
k,l
d
d
+

l(l + 1)

2
_

_
y
k,l
() = 0 (2.119)
and the condition
y
k,l
(0) = 0. (2.120)
. Solutions in the form of power series
We expect the solution in the following form
y
k,l
() =
s

q=0
c
q

q
(2.121)
where by denition
c
0
0 (2.122)
The condition y
k,l
(0) = 0 implies that s > 0. We rst calculate the derivatives
d
d
y
k,l
() =

q=0
(q + s)c
q

q+s1
(2.123)
d
2
d
2
y
k,l
() =

q=0
(q + s)(q + s 1)c
q

q+s2
(2.124)
and we substitute these into the eigenvalue equation
_

_
d
2
d
2
2
k,l
d
d
+

l(l + 1)

2
_

_
y
k,l
() = 0 (2.125)
to get

q=0
(q + s)(q + s 1)c
q

q+s2
2
k,l

q=0
(q + s)c
q

q+s1
+

l(l + 1)

q=0
c
q

q+s
= 0 (2.126)
In order for this equation to be zero, all its coefcients (at each power of ) must be
zero.
The lowest order term is
s2
. By taking its coefcient as zero we get (homework)
[l(l + 1) + s(s 1)] c
0
= 0 (2.127)
which is satised, since c
0
0, by the following relations

s = l + 1
s = l
(2.128)
and we choose as physically acceptable the condition
s = l + 1
(the other solution would be diverging for 0).
By setting the coefcients of the general term in
q+s2
we obtain the recurrence
(homework)
q(q + 2l + 1)c
q
= 2

(q + l)
k,l
1

c
q1
(2.129)
If we x c
0
, we can calculate using this recursion all the other coefcients of the
series c
1
, c
2
, ... c
q
.
Since c
q
/c
q1
0 as q , the series is convergent for all q.
Thus we have determined, for any value of
k,l
, the solution of the eigenvalue
equation for y
k,l
() with the condition y
k,l
(0) = 0.
c. ENERGY QUANTIZATION. RADIAL FUNCTIONS
We require the preceding solution to have correct, i.e. physically acceptable, asymp-
totic behavior for q . In this limit, the equation
q(q + 2l + 1)c
q
= 2

(q + l)
k,l
1

c
q1
(2.130)
reduces to
q
2
c
q
2q
k,l
c
q1
(2.131)
which implies that
c
q
c
q1

q
2
k,l
q
(2.132)
Now consider
e
2
k,l
=

q=0
d
q

q
(2.133)
where
d
q
=

2
k,l

q
q!
(2.134)
This implies that
d
q
d
q1
=
2
k,l
q
(2.135)
That is the series for y
k,l
() being considered behaves like e
2
k,l
and thus
u
k,l
() = e

k,l
y
k,l
() = e
+
k,l
(2.136)
which is not physically acceptable.
Consequently, we must reject all cases in which the expansion
y
k,l
() =
s

q=0
c
q

q
(2.137)
is an innite series.
That is the only possible values of
k,l
are those for which the expansion above
reduces to a polynomial.
u
k,l
is than physically acceptable since its asymptotic behavior is dominated by e

k,l
.
Therefore we need an integer k such that r.h.s. of the equation
q(q + 2l + 1)c
q
= 2

(q + l)
k,l
1

c
q1
(2.138)
goes to zero as q = k. Then c
q
= 0 for q k.
For xed l, we label the corresponding values of
k,l
by this integer (k 1 as c
0
never
goes to zero).
By the equation above we have

k,l
=
1
k + l
(2.139)
For a given l, the only negative energies possible are
E
k,l
=
E
I
(k + l)
2
; k = 1, 2, 3, . . . (2.140)
y
k,l
() is therefore a polynomial whose term of the lowest order is
l+1
and whose
term of the highest order is
k+l
.
The various coefcients can be calculated in terms of c
0
by the recursion
c
q
=
2(k q)
q(q + 2l + 1)(k + l)
c
q1
(2.141)
or alternatively by the formula
c
q
= (1)
q

2
k + l

q
(k 1)!
(k q 1)!
(2l + 1)!
q!(q + 2l + 1)!
c
0
(2.142)
u
k,l
() is then given as e

k,l
y
k,l
() and c
0
is determined by the normalization condi-
tion

0
dr

u
k,l
(r)

2
= 1 (2.143)
Finally we obtain the true functions R
k,l
(r) by
u
k,l
(r)
r
.
Examples:
R
k=1,l=0
(r) = 2

a
0

3/2
e
r/a
0
(2.144)
R
k=2,l=0
(r) = 2

2a
0

3/2

1
r
2a
0

e
r/2a
0
(2.145)
R
k=1,l=1
(r) =

2a
0

3/2
1

3
r
a
0
e
r/2a
0
(2.146)
4. Discussion of the results
a. ORDER OF MAGNITUDE OF ATOMIC PARAMETERS
The ionization energy E
I
and the Bohr radius a
0
play important roles in giving an
order of magnitude of the energies and spatial extensions of the wavefunctions
E
I
=
1
2

2
c
2
(2.147)
a
0
=
1

C
(2.148)
where
=
e
2
c
=
q
2
2
0
c

1
137
(2.149)

C
=

c


m
e
c
3.8 10
3
(2.150)
The Bohr radius a
0
is about 100 the Compton wavelength
C
of electron.
The ionization potential E
I
10
5
10
4
c
2
where the rest-mass energy
c
2
m
e
c
2
0.51 10
6
eV (2.151)
which implies
E
I
m
e
c
2
(2.152)
This condition justies our choice of non-relativistic Schr odinger equation to describe
the hydrogen atom.
b. ENERGY LEVELS
. Possible values of the quantum numbers; degeneracies
For a xed l, there exist an ininite number of possible energy values with k = 1, 2, 3...
and each of these is at least (2l+1)-fold degenerate. This is the essential degeneracy.
recall that this follows from the fact that the radial wavefunction depends on l but not
on m.
There exist accidental degeneracies when E
k,l
= E
k

,l
(l l

) if k + l = k

+ l

.
E
k,l
depends on (k + l) rather than k and l separately (only for hydrogen). We set
n = k + l (2.153)
which we call principal quantum number.
The energy levels are then
E
n
=
1
n
2
E
I
(2.154)
Since k 1, there is only a nite number of the values of l associated with the same
n, that is, if n is xed l = 0, 1, ..., n 1.
The shell n contains n subshells, each with (2l + 1) orthogonal states.
The total degeneracy of the level n is given as
g
n
=
n1

l=0
(2l + 1) = 2
(n 1)n
2
+ n = n
2
(2.155)
. Spectroscopic notation
The energy shells are labelled by n = 1, 2..or by the letters K, L, .... The subshells are
labelled by the corresponding number n followed by l in the spectroscopic notation:
l = 0 s
l = 1 p
l = 2 d
l = 3 f
l = 4 g
.
.
.
.
.
.
(2.156)
alphabetical order (2.157)
Example:
The ground state is K shell with 1s subshell, the rst excited state is L shell with the
subshells 2s and 2p, etc.
The hydrogen atom energy levels
c. WAVE FUNCTIONS
Wavefunctions are labeled by the quantum numbers n, l, and m which uniquely char-
acterize the eigenfunctions
n,l,m
(r) of the C.S.C.O.

H,

L
2
, and

L
z
.
. Angular dependence
the angular dependence is given by the spherical harmonics Y
m
l
(, )
. Radial dependence
Since n = k + l, we can label the radial wavefunctions by n and l (rather than k and l)
R
k=1,l=0
R
n=1,l=0
; (2.158)
R
k=2,l=0
R
n=2,l=0
; (2.159)
R
k=1,l=1
R
n=2,l=1
(2.160)
the behavior of R
n,l
(r) around r = 0 is r
l
, so only states belonging to s subshell (l = 0)
give a nonzero probability of presence at the origin.
The greater l is, the larger is the region around proton with negligible probability of
nding an electron. This has interesting physical consequences (hyperne struc-
ture,...).
. Formula for successive Bohr radii r
n
= n
2
a
0
Let us consider various states with l = n 1, and calculate variation of probability
density with r for each of the preceding levels in an innitesimal solid angle d about
a xed direction of polar angles and
d
3
P(r, , ) =

n,l,m
(r, , )

2
r
2
drd (2.161)
=

R
n,l
(r)

2
r
2
dr

Y
m
l
(, )

2
d (2.162)
where the term

R
n,l
(r)

2
r
2
dr is the probability density between r and r + dr.
The condition l = n 1 implies k = n l = 1, so R
n,l
(r) contains only one term in
(r/a
0
)
n1
and the probability density
f
n
(r) =
r
2
a
2
0
_

r
a
0

n1
e
r/na
0
_

_
2
(2.163)
=

r
a
0

2n
e
2r/na
0
(2.164)
this function has a maximum for
r = r
n
= n
2
a
0
(2.165)
which is the Bohr radii of the Bohr orbit corresponding to the energy E
n
.
The wavefunctions of the lowest energy levels:
1s level
n=1,l=0,m=0
=
1

a
3
0
e
r/a
0
2s level
n=2,l=0,m=0
=
1

8a
3
0

1
r
2a
0

e
r/2a
0
2p level

n=2,l=1,m=1
=
1
8

a
3
0
r
a
0
e
r/2a
0
sin e
i

n=2,l=1,m=0
=
1
4

2a
3
0
r
a
0
e
r/2a
0
cos

n=2,l=1,m=1
=
1
8

a
3
0
r
a
0
e
r/2a
0
sin e
i
THE ISOTROPIC THREE-DIMENSIONAL HARMONIC OSCILLATOR
(Complement B
VII
)
Our objectives are:
1. Solving the radial equation
2. Finding energy levels and stationary wave functions
Consider a spinless particle of mass subjected to the potential
V(x, y, z) =
1
2

2
x
x
2
+
2
y
y
2
+
2
z
z
2

(2.166)
where

x
=
y
=
z
= (2.167)
The Hamiltonian is given as

H =

P
2
2
+ V

(2.168)
The standard solution relies on separating x, y and z coordinates in the coordinate
representation and solving the system in a way analogous to solving the harmonic
oscillator in one dimension. The energy eigenvalues found are
E
n
=

n +
3
2

(2.169)
their degree of degeneracy is
g
n
=
1
2
(n + 1)(n + 2) (2.170)
and the eigenfunctions associated with the eigenvalue E
n
, n = n
x
= n
y
= n
z
, are

n
x
,n
y
,n
z
(x, y, z) =
_

_
3/4
1

2
n
x
+n
y
+n
z
n
x
!n
y
!n
z
!
e

2
2

x
2
+y
2
+z
2

(2.171)
H
n
x
(x)H
n
y
(y)H
n
z
(z) (2.172)
where
=

, (2.173)
n = n
x
+ n
y
+ n
z
(2.174)
Since the oscillator is isotropic we can use the spherical coordinates; the potential
becomes a central potential
V(r) V(r) =
1
2

2
r
2
(2.175)
C.S.C.O. is given by

H,

L
2
and

L
z
.
1. Solving the radial equation
_

2
2
1
r
d
2
dr
2
r +
1
2

2
r
2
+
l(l + 1)
2
2r
2
_

_
R
k,l
(r) = E
k,l
R
k,l
(r) (2.176)
R
k,l
(r) =
1
r
u
k,l
(r) (2.177)

k,l
=
2E
k,l

2
(2.178)
_

_
d
2
dr
2

4
r
2

l(l + 1)
r
2
+
k,l
_

_
u
k,l
(r) = 0 (2.179)
We also have to add the condition
u
k,l
(0) = 0 (2.180)
to get the physically acceptable behavior of the wavefunction at the origin r = 0.
Considering the asymptotic behavior for r simplies the eigenvalue equation:
_

_
d
2
dr
2

4
r
2
_

_
u
k,l
(r)

r 0 (2.181)
whose two solutions are e

2
r
2
/2
and e

2
r
2
/2
, however only the latter is physically
acceptable as it does not diverges for large r.
We therefore seek the eigenfunctions in the form
u
k,l
(r) = e

2
r
2
/2
y
k,l
(r) (2.182)
y
k,l
(r) must satisfy
d
2
dr
2
y
k,l
2
2
r
d
dr
y
k,l
+

k,l

2

l(l + 1)
r
2

y
k,l
(r) = 0 (2.183)
y
k,l
(0) = 0 (2.184)
We expand y
k,l
(r) into a power series
y
k,l
(r) = r
s

q=0
a
q
r
q
(2.185)
where a
0
is by denition nonzero
a
0
0 (2.186)
We substitute y
k,l
(r) into the eigenvalue equation. The term of the lowest order is
r
s2
. Its coefcient is zero if
[s(s 1) l(l + 1)] a
0
= 0 (2.187)
which implies the physically acceptable (to satisfy y
k,l
(0) = 0) solution
s = l + 1 (2.188)
The next term in the expansion is r
s1
and its coefcient equals to
[s(s + 1) l(l + 1)] a
1
(2.189)
Since s is xed already, the coefcient can go to zero only if
a
1
= 0 (2.190)
The general term in r
q+s
is zero if

(q + s + 2)(q + s + 1) l(l + 1)

a
q+2
(2.191)
+

k,l

2
2
2
(q + s)

a
q
= 0 (2.192)
or
(q + 2) (q + 2l + 3) a
q+2
=

(2q + 2l + 3)
2

k,l

a
q
(2.193)
This recursion implies that all coefcients a
q
of rank q = odd are zero.
Coefcients of even rank are proportional to a
0
.
If no coefcients on r.h.s. go to zero, then y
k,l
(r) has the form of an implicit power
series for which
a
q+2
a
q

q
2
2
q
(2.194)
The behavior of the coefcients is the same as for the exponential function
e

2
r
2
=

p=0
c
2p
r
2p
(2.195)
with
c
2p
=

2p
p!
(2.196)
Then
c
2p+2
c
2p

p
2
2
p
(2.197)
and in this case the y
k,l
(r) would be dominated by e

2
r
2
which is not physically ac-
ceptable.
Physically acceptable cases are those in which there exists an even integer k, posi-
tive or zero, such that

k,l
= (2k + 2l + 3)
2
(2.198)
so the coefcients of the recursion of even rank greater than k are zero. Conse-
quently the series for y
k,l
(r) = r
s

q=0
a
q
r
q
must be nite and thus reduces to a
polynomial, and the radial function u
k,l
(r) decreases exponentially as r goes to inn-
ity.
2. Energy levels and stationary wave functions
The energy eigenvalues are
E
k,l
=

k + l +
3
2

(2.199)
where k is a positive integer or zero. Since E
k,l
actually depends on
n = k + l (2.200)
we can rewrite it as
E
k,l
=

n +
3
2

(2.201)
where k is an even positive integer or zero and l is any non-negative integer.
Thus n can take only integral values, positive or zero:
(k, l) = (0, n), (2, n 2), . . . , (n 2, 2), (n, 0) if n is even (2.202)
(k, l) = (0, n), (2, n 2), . . . , (n 3, 3), (n 1, 1) if n is odd (2.203)
This implies the values of l:
n = 0 : l = 0
n = 1 : l = 1
n = 2 : l = 0, 2
n = 3 : l = 1, 3
n = 4 : l = 0, 2, 4
(2.204)
E
n
= (n +
3
2
) =
3
2
,
5
2
,
7
2
,
9
2
,
11
2
, ...
For each pair (k, l) there exist one and only one radial wavefunction u
k,l
(r).
There is (2l + 1) eigenfunctions of

H,

L
2
and

L
z
:

k,l,m

=
1
r
u
k,l
(r)Y
m
l
(, ) (2.205)
and consequently the degree of degeneracy
g
n
=

l=0,2,...,n
(2l + 1) if n is even (2.206)
g
n
=

l=1,3,...,n
(2l + 1) if n is odd (2.207)
This specically yields
for even n : g
n
=
n/2

p=0
(4p + 1) =
1
2
(n + 1)(n + 2) (2.208)
for odd n : g
n
=
(n1)/2

p=0
(4p + 3) =
1
2
(n + 1)(n + 2) (2.209)
For each of the pair (k, l), we have one and only one u
k,l
(r) (to within a factor a
0
), and
thus (2l + 1) common eigenfunctions of

H and

L
2
with eigenvalues E
n
and l(l + 1)
2
.
Example: wavefunctions for the three lowest energy levels
(i) E
0
=
3
2

k = l = 0 (2.210)
y
0,0
(r) reduces to a
0
r where a
0
is determined by normalization

0,0,0

=
_

_
3/4
e

2
r
2
/2
(2.211)
The ground state is non-degenerate.
(ii) the rst excited state E
1
=
5
2

This state is three-fold degenerate

k = 0
l = 1
(2.212)
with y
0,1
(r) = a
0
r
2
.
The three eigenfunctions are

0,1,m

8
3

3/2

1/4
re

2
r
2
/2
Y
m
1
(, ) m = 1, 0, 1 (2.213)
The spherical harmonics Y
m
l
(, ) are such that
rY
0
1
(, ) =

3
4
z (2.214)
r

Y
1
1
Y
1
1

3
4
x (2.215)
r

Y
1
1
+ Y
1
1

= i

3
4
y (2.216)
and the Hermite polynomial of order 1 is
H
1
(u) = 2u (2.217)
so that the functions
0,1,m
are related to the functions
n
x
,n
y
,n
z
of the basis given by
the Hermite polynomials (Eq. (2.172)) by the equations

n
x
=0,n
y
=0,n
z
=1
=
k=0,l=1,m=0
(2.218)

n
x
=1,n
y
=0,n
z
=0
=
1

k=0,l=1,m=1

k=0,l=1,m=1

(2.219)

n
x
=0,n
y
=1,n
z
=0
=
i

k=0,l=1,m=1
+
k=0,l=1,m=1

(2.220)
(iii) the second excited state E
2
=
7
2

This state is six-fold degenerate, and k and l can take the values
k = 0, l = 2 (2.221)
k = 2, l = 0 (2.222)
The function y
0,2
(r) is a
0
r
3
, and the function y
2,0
(r)
y
2,0
(r) = a
0
r

1
2
3

2
r
2

(2.223)
the six basis functions in the eigenspace associated with E
2
are of the form

0,2,m

16
15

3/2

1/4

2
r
2
e

2
r
2
/2
Y
m
2
(, ) (2.224)

2,0,0

3
2

3/2

1/4

1
2
3

2
r
2

2
r
2
e

2
r
2
/2
(2.225)
Through the explicite expressions for the spherical harmonics and the Hermite poly-
nomials we can prove the relations:

k=2,l=0,m=0
=
1

n
x
=2,n
y
=0,n
z
=0
+
n
x
=0,n
y
=2,n
z
=0
+
n
x
=0,n
y
=0,n
z
=2

k=0,l=2,m=2
+
k=0,l=2,m=2

=
1

n
x
=2,n
y
=0,n
z
=0

n
x
=0,n
y
=2,n
z
=0

k=0,l=2,m=2

k=0,l=2,m=2

= i
n
x
=1,n
y
=1,n
z
=0
1

k=0,l=2,m=1

k=0,l=2,m=1

=
n
x
=1,n
y
=0,n
z
=1
1

k=0,l=2,m=1
+
k=0,l=2,m=1

= i
n
x
=0,n
y
=1,n
z
=1

k=0,l=2,m=0
=
2

n
x
=0,n
y
=0,n
z
=2

1
2

n
x
=2,n
y
=0,n
z
=0

1
2

n
x
=0,n
y
=2,n
z
=0